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RENEWABLE ECO-FRIENDLY POLY(LACTIC ACID) NANOCOMPOSITES FROM WASTE SOURCES

Final Report Summary - ECLIPSE (RENEWABLE ECO-FRIENDLY POLY(LACTIC ACID) NANOCOMPOSITES FROM WASTE SOURCES)

Executive Summary:

Not only society but also Governments are highly concerned about the environmental issues, and hence there is an increasing interest in the development of alternative sources for chemicals, plastics and energy. Thus, the main objective of ECLIPSE project, funded by the European Commission within the 7th Framework Programme, was to develop novel waste derived packaging concepts unrelated to fossil fuels and to the food chain by the revalorization of biomass waste materials for the production of PLA matrix and different nanofillers extracted from banana plants and crustaceans shell wastes.
In the ECLIPSE project, it was addressed the above issues by the research and development of i) novel 100% biodiesel-algal-waste based poly (lactic acid), ii) 100% waste-based bionanofillers from residual waste from banana plantations, and shells of shrimp and crab from the seafood industry, and iii) tailored inorganic fillers from over-abundant sources. Main achievements of the project are summarized bellow:
At the novel 100% biodiesel-algal-waste based poly (lactic acid), work was based on:
• The research on the best microalgae strain based on their biochemical composition.
• The evaluation of the best cultivation procedures for industrial scaling-up.
• The research on carbohydrates extraction, enzymatic fermentation process and PLA polymerization and the scaling up of all the processes.
At the 100% waste-based bionanofillers from biomass waste from banana plantations, and shells of shrimp and crab from the seafood industry, work is based on:
• The isolation of cellulose pulp from banana wastes and chitin from crustaceans shells.
mechanical and iii) using ionic liquids.
• The functionalization/modification of cellulose and chitin nanobiofillers.
• The production of cellulose and chitin nanofillers by three different approaches i) chemical, ii)
At the tailored inorganic fillers from over-abundant sources, work is based on the functionalization of:
• Inorganic silicates for gas barrier properties.
• Metallic oxide nanoparticles for light-barrier properties.
• Inorganic microfillers for thermal stability and cost reduction.
To put the cap on this intensive research effort on materials, novel dispersion technologies have been developed to provide a successful move of the materials towards industrialization, with a high focus on liquid feeding extrusion mechanisms in the presence of compatibilizing and plasticizing agents, to provide top performing masterbatches and compounds.
ECLIPSE project has reached to an end once these materials and processes to reach real industrial application. To ease developed technologies reach the serialized state, two end-users (one multinational and one SME) has introduced the project materials and processing technologies into targeted applications:
• Agricultural bags, being this the flagship product of BANACOL’s plastic factory.
• Flexible pouches for moist soft wipes and cleaning clothes, as a multilayered product with high requirements from BIOPAC.
Finally, it has successfully obtained different PLA based bioplastics for the two target applications. In addition of being 100% biobased, the materials used in the manufacture of these products, are compostable, which is an incentive for the commercial exploitation of these results.
In addition of these results, dissemination activities included a workshop, conferences and journal papers, a newsletter and press releases, and a dedicated project website: http://www.eclipseproject.eu.

Project Context and Objectives:
At current consumption levels, known recoverable crude oil reserves will dry up in approximately 30 years. Therefore, it is essential to plan these technical and economic upheavals by replacing crude oil-sourced polymers and fuels with truly renewable ones. Efforts to shift from oil-based to biomass-based plastics such as poly(lactic acid) (PLA) are increasing as companies look for ways to protect the environment and create sustainable societies.
Poly(lactic acid) is a compostable polymer derived from renewable edible sources (corn and sugar beet) and has the highest potential for a commercial major scale production of renewable packaging materials. However, a report by the European Commission published in December 2010 highlights the concerns of land grown crops based biofuels and bioplastics as they increase the amount of land devoted to agriculture worldwide and increase the price of agricultural products like corn, wheat, fats and oils. In contrast, algae are not edible and currently represent a very promising area of research right now as researchers are now looking out to the sea for future polymer and fuel feedstocks.
ECLIPSE aimed at decreasing the production cost of both PLA and algae-derived biodiesel by increasing the added value of algae biodiesel biomass waste via its revalorization into producing lactic acid.
The objective of ECLIPSE was to develop novel waste derived packaging concepts unrelated to fossil fuels and to the food chain. The ECLIPSE approach intended to revalorize waste materials for the production of not only the PLA matrix but also to reinforce the PLA matrix with non-edible functionalized waste nanofillers extracted from banana plants, almond shells and crustacean shell wastes .

Today packaging accounts for 70% of the PLA market. For some of the more demanding film-packaging applications, the brittleness of PLA and its poor thermal resistance and limited gas barrier properties have prevented its complete access to such applications. It is expected that the performance improvement to be developed during the ECLIPSE project will allow the use of PLA in two key markets: the household sachet and the agricultural bags markets.
The main goals of ECLIPSE are captured in the following particular scientific and technical objectives to be achieved in the project:
o Extraction and purification of lactic acid from the waste of algae biodiesel biomass production.
o Development of new biogenic PLA grade derived from lactic acid from algae waste.
o Extraction, purification and functionalization of polysaccharide nanofillers from natural waste materials:
- Cellulose nanofillers from banana plant and almond shell wastes.
- Chitin nanofibres from crustacean shells wastes.
o Functionalization of inorganic fillers to impart good compatibility with PLA:
- Organically modified nanoclays (Montmorillonites, sepiolite, halloysite) for improved gas barrier properties and thermal resistance.
- Inorganic nano TiO2, ZnO for light-barrier properties.
- Conventional microfillers (calcium sulphate, talc and others) to decrease cost.
o Development and validation of novel dispersion methods for nanofillers in liquid media prior to compounding and during extrusion compounding in the presence of compatibilizing agents, to maximise dispersion of nanofillers in PLA.
o Complete structural and physico-chemical characterization of the new PLA nanobiocomposite films.
o Improvement of PLA film properties to match those of 12 µ polyethylene terephthalate (PET) films currently used in household sachets multilayer structures:
- Oxygen transmission rate from 800 to 200 cc/m2/24 h (ASTM D-3985).
- Water vapor transmission rate from 380 to 50 g/m2/24 h (ASTM D-3985).
- Film heat shrinkage from 10% to 2.5% (ASTM D1204, 150 ºC 30 min).
- Ultraviolet light absorption (less than 3% transmission below 320 nm).
o Improvement of the properties of PLA films to match those of polyethylene films currently used for agricultural bags:
- Elongation at break from 17% to 190% (ASTM D-882).
- Impact resistance from 0.03 J to 2.3 J (ASTM D3420-94).
o Life Cycle Analysis (production, use, disposal/recycling) including cost analysis of new PLA-based packaging.
Household sachets
Plastic household sachets for dry and liquid consumer goods are very popular as they allow the production and sale of very convenient single portions. However, they present a significant waste problem and therefore the utilization of a renewable compostable polymer such as PLA for the fabrication of sachets is highly desirable. These sachets are made up of multilayer structures composed of at least two layers: an outer high gloss reverse printed 12 μ PET layer and an inner linear low density polyethylene (LLDPE) layer of 40 to 100 microns that allows heat sealing of the sachet and provides certain barrier to water vapor. For more sensitive products (those requiring higher barriers to water vapor and oxygen or light protection) a middle layer of vapor metalized bi-axially oriented polypropylene (vmBOPP) is also included in the sachet structure.

PLA is highly transparent and can be easily printed which makes it suitable for this application. However the light, gas barrier and thermal properties of PLA are far inferior from those of PET and therefore need to be improved during the course of ECLIPSE to match those of PET.
The final PLA-containing sachet multilayer structure, i.e. the number of layers and thicknesses of the layers will be dependent not only on the final barrier and mechanical properties achieved by ECLIPSE but also on the type of product that it will contain (more sensitive products require better barrier).
Agricultural bag
The agriculture industry uses millions of kilograms of polyolefins each year to produce plastic films and bags to cover plants and fruits. BANACOL, one of the most important multinational corporations in the production and commercialization of agro-industrial products, is particularly interested in a cost competitive renewable and compostable material to cover fruits during their growth. This will replace the actual oil-based non compostable polyolefin bags.
PLA, although compostable, is very brittle and cannot be easily transformed into plastic bags unless plasticized and reinforced to improve its impact resistance and elongation at break. It is the purpose of ECLIPSE to provide the agricultural market with a PLA-based sustainable and renewable plastic bag solution.
Our strategy to achieve these novel biogenic packaging concepts consists of a step-wise approach that integrates the work, expertise and facilities of all different partners. The industrial partnership has been designed to combine leading companies to supply the raw materials ALGAENERGY (algae), GALACTIC (lactic acid), FUTERRO (PLA), BANACOL (banana waste) and ANTARTIC (crustaceans waste) with sound research groups that are active on biopolymers, nanoparticles functionalization and dispersion (UMONS, CIDETEC, FRAUNHOFER, LTU, UPV/EHU, UPB, PUC) as well as a global end user PGG with multiple converting facilities for plastic packaging.

Project Results:
The project has been highly active and successful since its inception in April 2012.
Main activities, scientific and technical results and foreground generated are summarised in the paragraphs below.
Selection and cultivation of dual purpose algae
Overall, the algal biomass comprises three main components – carbohydrates, proteins and lipids. Depending on the particular strain and the growing conditions, algae show large differences in the percentages of these key macroconstituents: typically 25-40% of protein, 5-30% of carbohydrate and 10- 30% of lipids/oils, by dry weight.

Figure 4. The double purpose algae approach for biodiesel and lactic acid production.
The lipid fraction of the biomass can be used to produce biodiesel whereas the carbohydrates can be fermented to produce a biopolymer feed stock such as lactic acid as shown in Figure 4. Algae are the optimal non-edible source for second generation based PLA due to the fact that they are high in carbohydrates fermentable into LA.
ECLIPSE project optimized the strain selection and cultivation conditions in order to develop novel strains with good yields of both lactic acid and biodiesel. These novel strains contain carbohydrates easily fermentable into LA, such as high amylase and low amylopectin starches as well as cellulose free of hemi-cellulose.
For verifying the feasibility of the whole process 1 Kg of the selected alga waste from lipid extraction was used for obtaining lactic acid with positive results. The selected microalga was chosen based on the combination of different factors: accurate proportion between carbohydrates and lipids and fast growing rate at lab scale. However, this microalga was specifically cultivated for the project, since nowadays, despite of being technically feasible, the production of biodiesel from algae is not yet economically viable (See D2.7 section 4 Economic and Viability Study).
The difficulties found during this activity were related with the growing up of algae for the scaling up process. The criterion for the selection of the algae strain was the high content of this specific alga of fermentable sugars together with the high content of lipids. This selection was carried out at the beginning of the project and the selected alga seemed to be the perfect candidate at lab scale. However, when the scale up of the process was addressed, the performance of this strain during winter time came to light, being lower than expected. For solving this problem, two additional varieties of algae were studied in order to achieve the growing rate needed for the industrialization of the process. Specifically, one of the additional varieties had a very fast growing rate and high amounts of biomass could be achieved in a short term. However, none of these strains shown the concentration of fermentable sugars needed for the obtaining of lactic acid (page 17 of the attached pdf “ Core Periodic Report”). For the scaling up process 104 Kg of wet biomass of selected alga strain was produced for the obtaining of lactic acid.
Lactic acid from de-oiled algae biomass carbohydrate waste
Algae cake that is left over after extraction of oil for biodiesel (primarily composed of carbohydrates and proteins) can be converted into LA through fermentation of the sugars. This gives rise to the interesting possibility of producing both biodiesel and LA from the same algae.
The chemical composition (lipid, starch and carbohydrate ratios) of microalgae greatly depends not only on the strain selected but also on the growing conditions utilized.
During the project, lactic acid batches have been successfully obtained for their further polymerization into PLA (Figure 5).

Figure 5. Lactic acid from purified and impurified lactic acid.

Regarding the performance of the process studied at lab scale, the yield of each involved step results in a global yield in experimental conditions of 10% of the weight of dry matter that can be converted to lactic acid. These steps include hydrolysis, fermentation and purification:
• Hydrolysis yield (w/w): 17% of the alga weight can be converted to sugar.
• Fermentation Yield = 94%
• Purification : 62-65%
Thus, the global yield in experimental conditions, taking into account the different steps can be calculated as follow:
(0,17 X 0,94 X 0,635) X 100 = 10% of the weight of dry matter can be converted to lactic acid
As the raw material (wet alga) contains 20% of dry matter, it can be concluded that approximately 2% (w/w) of the wet material can be converted to lactic acid, that is to say, 100kg of wet alga provides 2kg of lactic acid (See D.2.6).
Regarding the PLA production, it is a multi-step process consisting on the following steps: oligomerization, cyclization, purification and polymerization.
For each step, the yield and the quality of the product were analyzed comparing with lactic acid from sugar beet.
• Oligomerization step is not LA purity dependent for the yield but for the quality (higher racemization & colour).
• Cyclization is dependent of LA purity for the yield and the quality (higher racemization & colour).
• Purification is LA purity dependent for the yield but not for the quality.
• Polymerization is not LA purity dependent for the yield and slightly for the quality (as purification allows reaching lactide polymer grade).

At the scale of work (lab scale), the global yield of PLA obtaining process was very low. In industrial conditions, the losses of materials involved in each step will be minimized due to the possibility of reusing and recycling of by-products.
Within ECLIPSE different samples of PLA from algae in powder form were produced (Figure 6).

Figure 6. PLA from algae.
After thermal, physical and mechanical analysis it can be concluded that both types of PLA, sugar beet PLA and algae derived PLA are equivalents. Both types of polymers show no significant differences in thermal behaviour, in terms of stability and thermal parameters such as Tg and Tm.
Functional inorganic fillers (FIF) to improve PLA performance
the specific functionalization of natural inorganic nano/microfillers such as nanoclays and metallic oxide nanoparticles, e.g. nanoTiO2 and nanoZnO that are either commercially available or purposely-synthesized in the framework of the ECLIPSE project, were used to compatibilize and to facilitate the dispersion in PLA endowing targeted properties to the resulting nanocomposites. These functionalized nano/microfillers will be incorporated into PLA to improve the properties of PLA and fulfill the application requirements of agricultural bags and household sachets.
Figure 7. SEM micrographs of ZnAl LDH at different magnifications.
Polysaccharide based nanofillers (PSN) to improve PLA performance
Plant based wastes were used as a source of cellulose nanofillers and the crustacean ones to isolate chitin nanofillers which can be useful for many applications. Their use for packaging applications in combination with biomass-based polymers as matrices, allows achieving a completely sustainable closed loop, as plants and sea animal wastes would be used for high-standing developments in this sector.

Figure 8. Height and amplitude AFM images of the banana nanofibers and the measured fibers dimensions
Scalability of materials and processes
With respect to the final requirements for agricultural bags and flexible pouches, specified formulations for each application had to be investigated, especially the requirements for the production of agricultural bags. The material needed to be strong but also flexible, with high melt strength for stable processing on a blown film line.

Figure 9. Blown film with cellulose nanofibre composition.

During the project, specific formulations adapted for the final applications were developed and the amounts of materials needed for validation trials were manufactured.
Validation of materials in the final application
The validation of the selected products, wipe pouches and agricultural bags, included the manufacturing process at the facilities of the end users and the material properties achievement. Both products were successfully manufactured and materials were validated with specific tests.
- Wipe pouches sachets
In the case of wipe pouches, the manufacturing process was especially complicated when the co-lamination of different layers (with different composition) was carried out. To overcome these difficulties, for the preparation of the second generation of validation materials, the same base material (PLA) was used in each layer, obtaining a good quality film.

Figure10. Scheme of wipe pouches manufacturing with ECLIPSE materials.
In terms of properties, the most restrictive for the final use of the product was the gas barrier properties. It has to be taken into account that in the objectives mentioned in the DoW (part B) the reference material was neat PLA, while during the project PLA has been modified with different additives in order to achieve a material that fulfils the requirements of the application in terms of processability, flexibility, etc. This deviation was already considered in the evaluation of the project’s risks and the production of a multilayer film was proposed as a contingency plan (See Section 1.3.3 Risk management and associated contingency plans, WP5: “Developed PLA based nanobiocomposites do not achieve targeted barrier properties”). In fact, the colamination with a SiOx coated PLA allowed the achievement of the targeted barrier properties (tables 1 and 2).
Table 1. Reference values for ECLIPSE materials.

Table 25. Gas barrier properties of ECLIPSE materials.

- Agricultural bags
This was the most challenging application, since the current material used for agricultural bags is PE and the machinery is adapted to this material. There was necessary a huge effort to adapt the process to the novel material based on PLA.
Because bags producing process was adjusted to a very different material, PE, the setting up of the parameters was not obvious. In fact, the first generation of materials developed within the project was not suitable for blow moulding process at industrial scale (even if at lab scale was possible to produce bags) and the adjustment of the compounds was carried out for the second generation. For that reason, the obtaining of agricultural bags was considered a success by itself.
Additionally, there was another challenge linked to the validation due to the amounts of materials involved in the manufacturing process. On one hand, for the setting up of the machine parameters around 200-300 Kg of compound was needed (100 Kg/hour).

Figure 11. Blow molding of ECLIPSE materials for agricultural bags.
On the other hand, regarding properties, the compostability was one of the most significant properties for the validation of the project materials. It was planned to test the compostability after field trials, but due to the fact that 12 weeks were necessary to the growing of the bananas, there was not enough time during the project life to carry out these tests. However, compostability was tested at lab scale verifying that ECLIPSE formulation was compostable.
Finally, it must be said that ECLIPSE agricultural bags were not able to resist the severe weather conditions in Colombia and the strong wind damaged prematurely the bags. It was suggested that a thicker bag will allow the use of ECLIPSE materials for this application and the influence of the thickness in the resistance of the material was investigated at lab scale with positive results. Unfortunately, there was not time during the project life to prepare the amounts of materials needed to carry out a new manufacturing of agricultural bags at end user facilities.
Validation is widely described in D6.1 D6.2 and 6.3 as well as in the Core Periodic Report, page 58 to 81.
LCA and cost analysis
PLA has been proven to be an environmental friendly bio-based raw material. When PLA is used for the production of films additives are needed. These additives often go along with a poor environmental performance. Therefore, accompanying research is required that focuses on the environmental performance of these additives. The development of bio-based softeners can also support the overall performance, also leading to reduced environmental impacts in the end-of-life stage. It needs to be analyzed whether nanomaterials also have the potential to contribute to a better performance.
Regarding costs, it can be summarized that final products are more expensive than current products used in each application. However, the benefits derived from the use of fully renewable and compostable materials can be an incentive for the commercial exploitation of these results.
1.4 Conclusions and recommendations
Although most of the objectives were achieved, some of them were very challenging and some recommendations for future projects should be proposed. Main conclusions and recommendations are described below:
• Dual purpose algae strains have been investigated for both lipids for biodiesel production and carbohydrates for lactic acid extraction. It has been demonstrated the technical feasibility of the process and a complete cycle has been carried out with the selected alga strain. This strain showed a high content in lipids and carbohydrates and a suitable growing rate. For the industrialization of the process, it should be necessary a deeper study on algae strain performance taking into account not only the lipids and carbohydrates content but also the growing rate along the different seasons.
Regarding the availability of raw material, nowadays there is not an industrial waste from algae used for biodiesel production due to the fact that currently it is not a competitive product comparing with fuel base diesel. In the future, if there is an industrial production of biobased fuel from algae, the whole valorization of the algae (not only for biodiesel and lactic acid, but also for pigments, antioxidants and other additives obtaining) will allow that the process becomes profitable. As the results gathered during this project showed that we can reasonably expect to extract 17 % of fermentable sugar from the selected algae, the one that turned to be best candidate, the maximum affordable price for the algae wastes becomes 0,04 € per kg of dry matter.
• The obtaining of lactic acid from carbohydrates of algae was achieved. The limiting step was the maximum content of carbohydrates that can be converted to fermentable sugars and that it was around 17% refered to the residual biomass after lipids extraction. Other steps involved such as fermentation and purification have rates at lab scale that can be high enough for an industrial process (94% for fermentation and 62-64% for purification process).
• PLA polymerization process from lactic acid obtained from algae was successfully achieved. At the scale of work in the project (lab scale) the global yield of PLA polymerization process was very low. In industrial conditions, the losses of materials involved in each step will be minimized due to the possibility of reusing and recycling of by-products. One of the most critical processes in PLA polymerization is the purification step, where the loss of material is a 35% for each stage. With the low amount of PLA obtained it was not possible to validate the product in a demonstrator. However it was demonstrated that PLA from algae was the same that commercial PLA from sugar beet in terms of thermal and mechanical properties, that is to say, once lactic acid is converted into PLA there was no differences in the final material due to the source of raw material used.
• Extraction of cellulose and chitin from biomass waste. Regarding cellulose, mechanical methods (combined with chemical treatments) have shown to be a scalable and cost effective methods comparing with ionic liquid extraction. Functionalization was successfully carried out in all cases and PLA nanocomposites were obtained by casting. However it was not a suitable modification for the preparation of nanocomposites by melt blending. To overcome this drawback a scalable method for the incorporation of PSN to PLA was addressed in the compounding.
Concerning chitin, an innovative method for obtaining chitin flour from crustacean shell is under evaluation for intellectual property protection. Additionally, other significant results obtained were the development of an easy method for tuning the dispersability of chitin nanocrystals in different solvents.
From an industrial point of view, the most challenging task was the preparation of 500 g of chitin nanocrystals supplied for the first trial of validation and additional 60 g for the second trial. Further investigation for the industrialization of the process should be necessary.
• Inorganic filler functionalization was also achieved at the scale needed for validation. The most significant results were the improvement of the properties of the nanocomposites due to the incorporation of functionalized nanofillers and two scientific papers were prepared with these results. Some of the methods used for the functionalization can be used at industrial level.
• Regarding compounding, a scalable method for the incorporation of chitin and cellulose nanofillers was used in the preparation of masterbatch. Additionally, during the project the formulations suitable for each application were developed at lab scale. These formulations were scaled up and a ffirst generation of both types of compounds (for agricultural bags and for wipe pouches) were developed. These formulations were not suitable for the final applications in terms of processability. For that reason, improved formulations in both cases had to be developed and second generations of compounds with adapted properties for the targeted applications were used for validation trials. It should be useful for future projects to develop “base” compounds at industrial level in parallel with lab scale trials, in order to prevent possible deviations derived from the scale of work.
• Validation activities included the manufacturing of the final products at the end user facilities and the evaluation of the properties. In both cases, manufacturing was successfully carried out, despite of, in the case of agricultural bags, two different trials for being able to produce bags were necessary. In terms of properties, the main difficulties were found in the barrier properties achievement for wipe pouches sachets, and it was necessary the colamination with a SiOx coated PLA film. In the case of agricultural bags, the main difficulty was the weather conditions that damaged the bags. It was demonstrated at lab scale that the increase of the thickness could avoid these problems. Thus, in the future, it should be necessary an adjustment of the final formulations in order to fulfil all the requirements necessary for bananas cultivation.
The project has demonstrated that it is possible to obtain PLA from algae waste and to modify it by compounding with polysaccharides based nanofillers from renewable resources in order to obtain two different end products: agricultural bags and sachets for wipe pouches. In addition of being 100% renewable these products are compostable.

Potential Impact:
During the course of the project, several post-graduate students were trained. The expertise and skills thus developed has enhanced employment capability of young researchers in Europe.
Eclipse partners made a significant contribution to the dissemination of the project results as it was reflected in the amount of scientific papers publications that are listed below:
1. Mehmet Isik, Raquel Gracia, Lessié C. Kollnus, Liliana C. Tomé, Isabel M. Marrucho, and David Mecerreyes (2013). Cholinium-Based Poly(ionic liquid)s: Synthesis, Characterization, and Application as Biocompatible Ion Gels and Cellulose Coatings. ACS Macro Lett.,2 (11), pp 975–979.
2. Mehmet Isik, HaritzSardon, Miriam Saenz and David Mecerreyes.New amphiphilic block copolymers from lactic acid and cholinium building units.RSC Advances, 2014,4, 53407-53410.
3. Mehmet Isik, Raquel Gracia, Lessie C. Kollnus, Liliana C. Tome, Isabel M. Marrucho, D. Mecerreyes.Cholinium Lactate methacrylate: ionic liquid monomer for cellulose composites and biocompatible ion gels. Macromolecular Symposium 2014, 342, 21-24
4. Re, G.L. Benali, S., Habibi, Y., Raquez, J.-M. Dubois, P. Stereocomplexed PLA nanocomposites: From in situ polymerization to materials properties (2014) European Polymer Journal, 54 (1), pp. 138-150.
5. Pedro M. Carrasco, Sarah Montes, Ignacio García, MaryamBorghei, HuaJiang, Ibon Odriozola, Germán Cabañero, Virginia Ruiz. High-concentration aqueous dispersions of graphene produced by exfoliation of graphite using cellulose nanocrystals (2014) Carbon, 70, 157-163
6. Salaberria, A.M. Fernandes, S.C.M. Diaz, R.H. Labidi, J.Processing of α-chitin nanofibers by dynamic high pressure homogenization: Characterization and antifungal activity against A. niger(2015) Carbohydrate Polymers, 116, pp. 286-291.
7. Herrera, N., Mathew, A.P. Oksman, K. Plasticized polylactic acid/cellulose nanocomposites prepared using melt-extrusion and liquid feeding: Mechanical, thermal and optical properties(2015) Composites Science and Technology, 106, pp. 149-155.
8. J. Velásquez-Cock, J.-L. Putaux, M. Osorio, C. Castro, P. Gañán, R. Zuluaga. (Chapter Review) Nanocellulose: production and properties. In: “Cellulose and Cellulose Derivatives: Synthesis, Modification, Nanostructure and Applications”. Nova Science Publishers, Inc., New York, USA, (2015).
9. "Ionic Liquids and Cellulose: Dissolution, Chemical Modification and Preparation of New Cellulosic Materials" by M. Isik, H. Sardon and D. Mecerreyes in "Handbook of Ionic Liquids&Polymers" Springer, Publication date 2015, Editor David Mecerreyes
10. Natalia Herrera, Asier M. Salaberria, Aji P. Mathew and Kristiina Oksman. Plasticized polylactic acid nanocomposites films with cellulose and chitin nanocrystals prepared using extrusion and compression molding with two cooling rates: mechanical, thermal and optical properties. Submitted to Composites Part A (Nov 2014).
11. Sarah Montes, Pedro Mª Carrasco, Ibon Odriozola, Germán Cabañero, Hans Grande, Jalel Labidi, Virginia Ruiz. Synergistic reinforcement of poly(vinyl alcohol) nanocomposites with cellulose nanocrystal-stabilized graphene (Accepted in Composites Science and Technology. DOI 10.1016/j.compscitech.2015.05.018).
12. Ignacio Garcia, Itxaso Azcune, Pablo Casuso, Pedro M. Carrasco, Hans-J. Grande, German Cabañero, DimitriosKatsigiannopoulos, Eftychia Grana, Konstantinos Dimos, Michael A. Karakassides, Ibon Odriozola, Apostolos Avgeropoulos. Carbon nanotubes/chitin nanowhiskers aerogel achieved by quaternization-induced gelation (Submitted to Journal of applied polymer Science).
13. Natalia Herrera, Asier M. Salaberria, Hendrik Roch, Maximiliano A. Pino, Susana Fernandes, Jalel Labidi, Thomas Wodke, Deodato Radic, Kristiina Oksman. “Preparation and characterization of blown films based on plasticized poly lactic and chitin nanocrystals”. Under preparation (2015).
14. A. M. Salaberria, S.C.M. Fernandes, Jalel Labidi, Properties of poly(lactic acid)-based nanocomposites reinforced with functionalized α-chitin nanocrystals. Submitted to Journal of the Taiwan Institute of Chemical Engineer.
15. M. Pino, Asier M. Salaberria, J. Labidi, S. Fernandes, A. Leiva, M. Venegas, D. Radic. Optimisation of chitin extraction process. Under preparation (2015).
16. Hooshmand S, Aitomäki Y, Norberg N, Mathew A.P Oksman K. Dry spun single filament fibers using only cellulose nanofibers from bio-residue. ACS Applied Materials and Interfaces. Accepted 2015.
17. Haque Minhaz-Ul and Oksman K. "Bionanocomposites with Semi-IPNs Structure based on, Polyurethane and Benzyl Starch and Cellulose Nanofibres". To be submitted to Journal of Applied Polymer Science (2015).
ECLIPSE project participants contributed to different events related to the project topics in order to make a dissemination of the significant results of the project:
1. Oksman K. Nanocellulose activities at LTU, Cellulose Nanocomposite Summit. Kyoto, Japan (Invited speaker) 15 October 2012.

2. Oksman K. Bionanocomposites, Tomorrows Materials. Chalmers, Gothenburg, Sweden, 1-2 October 2013. (Invited speaker)

3. Castro C., Zuluaga R., Tabares M., Velazquez-cock J, Cardona S, Putaux J-L, Rojas O., Laine J., Gañan P. Reinforcing nanocellulose isolated from banana rachis and corn husk. 2013 TAPPI International Conference. 24-27 June 2013 (poster communication).

4. Castro C., Zuluaga R., Putaux J-L, Osorio M, Rojas O., Caro G, Gañan P. In-situ self-assembly and hydrophobization of Gluconacetobacter bacterial cellulose. 2013 TAPPI International Conference. 24-27 June 2013 (oral communication).

5. Susana C. M. Fernandes, Asier M. Salaberria, Jalel Labidi, Chitin nanocrystals: a unique source of functional materials, 11th International Conference of the European Chitin Society (EUCHIS 2013), May 2013, Porto, Portugal (poster communication).

6. Susana C. M. Fernandes, Asier M. Salaberria, JalelLabidi.,Chitin nanofillers: A major breakthrough for chitin applications, EPNOE 2013 International Polysaccharide Conference, 21-24 October, Nice, France (oral communication).

7. Natalia Herrera V, Aji P. Mathew and Kristiina Oksman. Preparation of Bionanocomposites.. Wallenberg Wood Science Center workshop on wood and cellulose. Stockholm, June 2013 (Poster presentation).
8. Synergistic Effect of cellulose nanocrystals and graphene on the properties of polymeric biocomposites. Sarah Montes, Pedro Mª Carrasco, Ibon Odriozola, Germán Cabañero, Jalel Labidi, Virginia Ruiz. 13th EWLP, Seville, 24-27 June 2014.
9. A.M. Salaberria, S.C.M. Fernandes, J. Labidi, Starch-based biocomposistes reinforced with chitin nanocrystals and nanofibers, 5th Workshop in Green Chemistry and Nanotechnologies in Polymer Chemistry, ECLIPSE Workshop&BIOPURFIL Workshop, July 9-11th, 2014 San Sebastian, Spain (poster communication)

10. Sarah Montes, Itxaso Azcune, Ibon Odriozola, Germán Cabañero, H. Grande, Jalel Labidi. Extraction of cellulose and lignin of banana racchies using ionic liquids”, 5th Workshop in Green Chemistry and Nanotechnologies in Polymer Chemistry, ECLIPSE Workshop&BIOPURFIL Workshop, July 9-11th, 2014 San Sebastian, Spain (poster communication)

11. Susana C.M. Fernandes, Asier M. Salaberria, JalelLabidi, Processing and properties of chitin nanoforms and their use in bionanocomposites, International Conference on Biobased Materials and Composites ICBMC14,May 13th-16th, 2014, Montréal, Canada (oral communication)

12. S.C.M. Fernandes, A.M. Salaberria, A. Alonso- Varona, T. Palomares, V. Zubillaga, J. Labid, Designing cell-compatible and antifungal genipin-cross-linked chitosan/chitin nanocrystals scaffolds for nanomedicine, 5th Workshop in Green Chemistry and Nanotechnologies in Polymer Chemistry, ECLIPSE Workshop & BIOPURFIL Workshop, San Sebastian, Spain, July 2014 (oral communication)

13. A. M. Salaberria, R. H. Diaz, J. Labidi, Susana C. M. Fernandes, Chitin Nanoforms: From Green Nanocomposites to Biomedical Applications, 2nd International conference on Bio-based Polymers and Composites-BiPoCo 2014, Visegrád, Hungary, August 2014 (oral communication)

14. Mehmet Isik, David Mecerreyes; Poly(L-lactide)-b-poly(2-cholinium lactate methacrylate) block copolymers: Synthesis, characterization and self-assembly. Oral communication in 5 th Workshop Green Chemistry and Nanotechnologies in Polymer Chemistry, San Sebastian 9-11 July 2014

15. Cristina Castro, Robin Zuluaga, Maria Tabares, Sandra Cardona, Jean-LucPutaux, Orlando Rojas and Piedad Gañan. Production of cellulose reinforcing elements from banana rachis and corn husk. 5th Workshop of Green Chemistry and Nanotechnologies in Polymer Chemistry, ECLIPSE Workshop, BIOPURFIL Workshop. July 9-11, 2014, Donostia-San Sebastian, Spain

16. Jorge Velásquez-Cock, Marlon Osorio, Cristina Castro, Lina Vélez, Piedad Gañán, Robin Zuluaga. Nanocellulose isolation from banana plants: effect of a second mechanical treatment. 5th Workshop Green Chemistry and Nanotechnologies in Polymer Chemistry, ECLIPSE Workshop, BIOPURFIL Workshop. July 9-11, 2014, Donostia-San Sebastian, Spain (poster communication).

17. M. Pino, A. Leiva, M. Venegas, D. Radic. Characterization of Chitin. 5th Workshop Green Chemistry and Nanotechnologies in Polymer Chemistry, ECLIPSE Workshop, BIOPURFIL Workshop. July 9-11, 2014, Donostia-San Sebastian, Spain.(Poster presentation).

18. J. Velásquez-Cock, C. Castro, J.M. Vélez, E. M. Cadena, P. Gañán, R. Zuluaga. Influence of a secondary mechanical treatment in the crystalline structure of cellulose nanofibers. American chemical society 247th Annual meeting. March 16-20, 2014. Dallas, TX, U.S.A (poster communication).

19. Jorge Velásquez-Cock, Piedad Gañán, Lina Velez, Cristina Castro, Marlon Osorio, Diana Jaramillo, Jean-LucPutaux, Robin Zuluaga. The physicochemical and thermal properties of nanocellulose isolated from banana pseudostem at different times of maturation. VIII Iberoamerican Congress on Pulp and Paper Research 2014. November 26-28, 2014, Medellín, Colombia (oral communication).

20. Herrera-Vargas N, Roggio G, and Oksman K. Toughening of cellulose nanofiber films. Oral presentation. 247thACS Conference. Dallas, March 2014.

21. Herrera-Vargas N, Mathew A.P and Oksman K. Manufacturing of PLA nanocomposites improving its toughness with plasticizer and cellulose nanofibres. Oral presentation. SPE ANTEC 2014. Las Vegas, April 2014.

22. Hooshmand S, Aitomäki Y, Mathew A.P Oksman K. Dry-spinning of continuous cellulose fibers using only nanofibers from a bio-residue. 5th Workshop Green Chemistry and Nanotechnologies in Polymer Chemistry. ECLIPSE Workshop, BIOPURFIL Workshop. Oral presentation.

23. Hooshmand S, Aitomäki Y, Mathew A.P Oksman K. Exploiting the self-assembly of cellulose nanofibers in wet and dry spun fibers. 247th ACS Conference. Dallas, March 2014. Oral presentation.

24. Hooshmand S, Aitomäki Y, Mathew A.P Oksman K. Native Cellulose and Matrix-Free Filaments Prepared By Dry Spinning Of Cellulose Nanofibers Obtained From A Bio-Residue. LTU-Monash Symposium on Bio-energy, Bio-materials and Energy Materials Wednesday 10 December 2014. Oral presentation.

25. Herrera-Vargas N, Mathew A.P and Oksman K. Extrusion of PLA nanocomposites using liquid feeding of cellulose/chitin nanocrystals. Abstract/ Oral presentation. 5th Workshop Green Chemistry and Nanotechnologies in Polymer Chemistry. Donostia-San Sebastian, Spain, 9-11 July, 2014.

26. Oksman K. High technology biocomposites from forest resources, Bioeconomy concept today and tomorrow. University of Oulu, Finland (invited speaker) April, 2014.

27. A.M. Salaberria, S.C.M. Fernandes, J. Labidi,Chitin nanofillers: from lobster shell wastes to new nanocomposite materials, 1stEPNOE Junior Scientes Meeting 2015, Wageningen, 19-20th January 2015 (oral communication).

28. I. Odriozola, S. Montes. Dibbiopack – NanoBarrier open seminar. InterCityHotel Frankfurt Airport, 1st October 2014. “Renewable eco-friendly poly(lactic acid) nanocomposites from waste sources” (Poster communication).

29. Lo Re G., Spinella S., Raquez J-M., Dubois Ph., Gross R.A. “Stereo-complexation and “Grafting from” approach to enhance nanoclay/PLA nanocomposites properties” PPS 30 CONFERENCE (CLEVELAND -06/2014. Oral communication.

30. Spinella S., Lo Re G., Liu B., Dorgan J., Habibi Y., Raquez J-M., Dubois Ph., Gross R. A., “Modification of cellulose nanocrystals with lactic acid for direct melt blending with PLA” PPS 30 CONFERENCE (CLEVELAND -06/2014). Poster communication.
Other dissemination means used by industrial partner were specific events for packaging industry:
- http://www.biopac.co.uk/news/28/biopac-announces-leading-role-in-eclipse

- http://resources.made-in-china.com/article/industry-view/IxfEZVtUVnlF/Biopac-Takes-Part-in-New-Sustainable-Packaging-Project/

- http://www.bioplasticsmagazine.com/en/online-archive/issues2013/201304.php

- http://sustainablepackaging.packaging-business-review.com/news/biopac-takes-part-in-new-sustainable-packaging-project-020713

- http://packagebr1.rssing.com/browser.php?indx=13074191&item=41

Regarding ECLIPSE workshop, the “5th Workshop Green Chemistry and Nanotechnologies in Polymer Chemistry” took place at the University of the Basque Country (UPV/EHU) on 9-11 July. http://www.ehu.es/en/web/5thworkshopgreenchemistry-nanotechnologies.

Finally, a dedicated project website, open to public, has been updated regularly: http://www.eclipseproject.eu

Exploitation:
Novel methods for the obtaining of materials along the value chain of the project have been developed. Some of them are under evaluation for patentability.
The project has demonstrated that it is possible to obtain PLA from algae waste and to modify it by compounding with polysaccharides based nanofillers from renewable resources in order to obtain two different end products: agricultural bags and sachets for wipe pouches. In addition of being 100% renewable these products are compostable.

List of Websites:
http://www.eclipseproject.eu